GB2077255A - Diacetals Used in Polyolefin Compositions - Google Patents
Diacetals Used in Polyolefin Compositions Download PDFInfo
- Publication number
- GB2077255A GB2077255A GB8112611A GB8112611A GB2077255A GB 2077255 A GB2077255 A GB 2077255A GB 8112611 A GB8112611 A GB 8112611A GB 8112611 A GB8112611 A GB 8112611A GB 2077255 A GB2077255 A GB 2077255A
- Authority
- GB
- United Kingdom
- Prior art keywords
- sorbitol
- composition according
- acetal
- benzaldehyde
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 27
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 29
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 239000000460 chlorine Substances 0.000 claims abstract description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052794 bromium Chemical group 0.000 claims abstract description 7
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 43
- 239000000600 sorbitol Substances 0.000 claims description 43
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 41
- -1 aliphatic olefin Chemical group 0.000 claims description 29
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 claims description 13
- 229940087101 dibenzylidene sorbitol Drugs 0.000 claims description 13
- 239000004743 Polypropylene Substances 0.000 claims description 12
- 229920001155 polypropylene Polymers 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- SONZVMBIAGVDAT-IYWMVGAKSA-N (3s,4s,5s,6r)-1,8-bis(3,4-dichlorophenyl)octa-1,7-diene-2,3,4,5,6,7-hexol Chemical compound OC([C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=CC=1C=C(Cl)C(Cl)=CC=1)=CC1=CC=C(Cl)C(Cl)=C1 SONZVMBIAGVDAT-IYWMVGAKSA-N 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000306 polymethylpentene Polymers 0.000 claims description 2
- 239000011116 polymethylpentene Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims 2
- 229920001519 homopolymer Polymers 0.000 claims 2
- 239000011885 synergistic combination Substances 0.000 abstract 1
- 235000010356 sorbitol Nutrition 0.000 description 37
- 239000000654 additive Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 150000001299 aldehydes Chemical group 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- HDUNAIVOFOKALD-RLCYQCIGSA-N (1s,2s)-1-[(4r)-2-(4-methylphenyl)-1,3-dioxolan-4-yl]-2-[(4s)-2-(4-methylphenyl)-1,3-dioxolan-4-yl]ethane-1,2-diol Chemical compound C1=CC(C)=CC=C1C1O[C@@H]([C@@H](O)[C@H](O)[C@H]2OC(OC2)C=2C=CC(C)=CC=2)CO1 HDUNAIVOFOKALD-RLCYQCIGSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 2
- ZETHHMPKDUSZQQ-UHFFFAOYSA-N Betulafolienepentol Natural products C1C=C(C)CCC(C(C)CCC=C(C)C)C2C(OC)OC(OC)C2=C1 ZETHHMPKDUSZQQ-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000003466 anti-cipated effect Effects 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 description 2
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000008395 clarifying agent Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- HEOKFDGOFROELJ-UHFFFAOYSA-N diacetal Natural products COc1ccc(C=C/c2cc(O)cc(OC3OC(COC(=O)c4cc(O)c(O)c(O)c4)C(O)C(O)C3O)c2)cc1O HEOKFDGOFROELJ-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HZVFRKSYUGFFEJ-YVECIDJPSA-N (2r,3r,4s,5r)-7-phenylhept-6-ene-1,2,3,4,5,6-hexol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=CC1=CC=CC=C1 HZVFRKSYUGFFEJ-YVECIDJPSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZWUSBSHBFFPRNE-UHFFFAOYSA-N 3,4-dichlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1Cl ZWUSBSHBFFPRNE-UHFFFAOYSA-N 0.000 description 1
- SUISZCALMBHJQX-UHFFFAOYSA-N 3-bromobenzaldehyde Chemical compound BrC1=CC=CC(C=O)=C1 SUISZCALMBHJQX-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- OVWYEQOVUDKZNU-UHFFFAOYSA-N m-tolualdehyde Chemical compound CC1=CC=CC(C=O)=C1 OVWYEQOVUDKZNU-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
- C08K5/1575—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
Abstract
The transparency of polyolefin compositions is improved by including a novel di-acetal formed between sorbital and benzaldehyde molecules, at least one of the benzaldehyde molecules being meta- or para- substituted with chlorine or bromine. Synergistic combinations with conventional diacetals are also disclosed.
Description
SPECIFICATION
Polyolefin Compositions
This invention relates to the improvement of the transparency of polyolefin compositions.
Polyolefins, for example polyethylene or polypropylene, have found a wide range of applications as packaging materials and containers in the form of films, sheets, or hollow articles, but because of their poor transparency, their use has been limited. In particular, they are unsuitable as packaging materials or containers for such articles as are described to be visible through them (e.g. cosmetics or foodstuffs).
Attempts have been made to improve the transparency of polyolefins by incorporating certain kinds of additives in them. For instance, para-t-butylbenzoic acid, its salts, low molecular weight waxy polyethylene, and low-molecular weight waxy polypropylene have been suggested as such additives.
These conventional additives, however, are unable to bring about a sufficient improvement of the transparency because they deteriorate the mechanical and chemical properties of the products, or have poor miscibility with the polyolefins.
More recently, as described in U.S. Patent Number 4,016,1 18, a polyolefin plastic composition having improved transparency and reduced molding shrinkage characteristics has been proposed which contains the compound dibenzylidene sorbitol. While this additive has been shown to be superior to those previously known for improving the transparency characteristics of polyolefin plastic compositions, it would be desirable to even further improve the transparency of such polyolefins without adversely affecting the mechanical and chemical properties of the final products. Accordingly, the present invention provides an additive which may improve the transparency of polyolefins even as compared to the previously known product dibenzylidene sorbitol which may not deteriorate the mechanical and chemical properties of the final products.
In the invention a polyolefin composition based on a polymer selected from aliphatic polyolefins and copolymers derived from at least one aliphatic olefin and one or more ethylenically unsaturated aliphatic comonomers has its transparency improved as a result of the inclusion of at least one diacetal formed between one molecule of sorbitol and one molecule of a first benzaldehyde of the formula
and one mole of a second benzaldehyde (which may be the same as or different from the first benzaldehyde) of the formula
wherein R, R1, R2, R3 and R4 are selected from hydrogen, lower alkyl, hydroxy, methoxy, mono- and dialkylamino, amino, nitro and halogen, with the proviso that at least one of R1, R2, R3 and R4 is chlorine or bromine.
The di-acetal may conveniently be represented as having the structure
However it should be appreciated with regard to the structural formula set forth above that while only the 1,3:2,4 isomer is represented, this structure is provided for convenience only and the invention is not limited to only isomers of the 1,3:2,4 type, but may include any and all other isomers as well as long as the compound contains two aldehyde substituents on the sorbitol moiety.
The di-acetal of the present invention may be a condensation product of sorbitol and benzaldehyde or a substituted benzaldehyde. At least one of the benzaldehyde or substituted benzaldehyde moieties is substituted in either or both of the meta and para positions with a halogen atom selected from chlorine and bromine. Substituents which may be employed on the substituted benzaldehyde moiety in any of the ortho, meta and para positions include, for instance, in addition to chlorine and bromine, which must be provided in either or both of the meta and para positions on at least one of the aldehyde substituents, lower alkyl, e.g. having from 1 to about 5 carbon atoms, hydroxy, methoxy, mono- and di-alkylamino, amino and halogen for instance other than chlorine and bromine.Preferred di-acetals of the present invention include di-p-chlorobenzylidene sorbitol; di-mchlorobenzylidene sorbitol; O-benzylidene-O-p-chlorobenzylidene sorbitol, di-m-bromobenzylidene sorbitol, and bis(3,4-dichlorobenzylidene) sorbitol.
The di-acetals of the present invention may be conveniently prepared by a variety of techniques, some of which are known in the art. Generally, such procedures employ the reaction of one mole of Dsorbitol with about two moles of aldehyde in the presence of an acid catalyst. The temperature employed in the reaction will vary widely depending upon the characteristics, such as melting point, of the aldehyde or aldehydes employed as a starting material in the reaction. The reaction medium may be an aqueous medium or a non-aqueous medium. One very advantageous method which can be employed to prepare the di-acetals of the invention is described in U.S. Patent No. 3,721,682, to Murai et al. (New Japan Chemical Company Limited), the disclosure of which is hereby incorporated herein by reference.While the disclosure of the patent is limited to benzylidene sorbitols, it has been found that the di-acetals of the present invention may also be conveniently prepared by the method described therein.
The di-acetals of sorbitol of the present invention prepared by the above techniques may contain a minor or even a major portion of by-product mono-acetal and tri-acetal as impurities. Although it may not always be necessary to remove these impurities prior to incorporation of the di-acetal into the polyolefin, it may be desirable to do so and such purification may serve to enhance the transparency of the resin produced thereby. Purification of the di-acetal may be accomplished, for instance, by removal of tri-acetal impurities by the extraction thereof with a relatively non-polar solvent. By removal of the impurities, the product may be purified so that the amount of di-acetal in the additive composition contains at least about 90 percent and even up to about 95 percent di-acetal or more.
As illustrated in the Figure with respect to the specific compound di-p-chlorobenzylidene sorbitol, the proportion of di-acetal in the composition of this invention is an amount sufficient to improve the transparency of the composition, generally from about 0.01 to about 2 percent by weight, preferably about .1 to about 1 percent by weight, based upon the total weight of the composition may be provided. When the content of di-acetal is less than about 0.01 percent by weight, the resulting composition may not be sufficiently improved in respect to transparency characteristics. When the content of di-acetal is increased beyond about 2 percent by weight, no additional advantage can be observed.
The polyolefin polymers of the present invention may include aliphatic polyolefins and copolymers containing at least one aliphatic olefin and one or more ethylenically unsaturated comonomers. Generally the comonomer if present will be provided in a minor amount, e.g., about 10 percent or less or even about 5 percent or less, based upon the weight of the polyolefin. Such comonomers may serve to assist in clarity improvement of the polyolefin, or they may function to improve other properties of the polymer. Examples include acrylic acid and vinyl acetate, etc.Examples of olefin polymers whose transparency can be improved conveniently according to the present invention are polymers and copolymers of aliphatic monoolefins containing 2 to about 6 carbon atoms which have an average molecular weight of from about 10,000 to about 500,000, preferably from about 30,000 to about 300,000, such as polyethylene, polypropylene, crystalline ethylenepropylene copolymer, poly( 1 -butene), and polymethylpentene. The polyolefins of the present invention may be described as basically linear, regular polymers which may optionally contain side chains such as are found, for instance, in conventional, low density polyethylene.
The olefin polymer or copolymer used in the composition of the present invention is crystalline, and the diffraction of light caused by micro crystals contained in it is considered to be responsible for the deterioration of the transparency of the polymer. It is thought that the di-acetal functions in the composition to reduce the size of the microcrystals thereby improving the transparency of the polymer.
The composition of the present invention can be obtained by adding a specific amount of the diacetal directly to the olefin polymer or copolymer, and merely mixing them by any suitable means generally prior to melt extrusion or molding. Alternatively, a concentrate containing as much as about 10 percent by weight of the di-acetal in a polyolefin masterbatch may be prepared and be subsequently mixed with the resin.
Other additives such as a transparent coloring agent or plasticizers (e.g., dioctyl phthalate, dibutyl phthalate, dioctyl sebacate, or dioctyl adipate), can be added to the composition of the present invention so long as they do not adversely affect the improvement of transparency of the product. It has been found that plasticizers such as those exemplified above may in fact aid in the improvement of the transparency by the di-acetal.
With regard to other additives it may also be desirable to employ the di-acetals disclosed above in combination with other conventional additives having known transparency improving effects such as, for instance, para-t-butylbenzoic acid, its salts, low molecular weight waxy polypropylene and the like. It may even be desirable to provide the particular di-acetals of the present invention in the polyolefin composition in combination with the previously described dibenzylidene sorbitol additive disclosed in U.S. 4,01 18. In such applications, generally at least about 10 percent, preferably about 25 percent, or even about 50 percent or more of the clarity improving component will be the di-acetals of the present invention, with the remainder being comprised of other known clarifying agents, plasticizers, etc.
The composition of the present invention is suitable as a packing material and container material for cosmetics and foodstuffs because it gives films, sheets or hollow articles having improved transparency characteristics and superior mechanical and chemical properties.
The following examples further illustrate the present invention. All parts and percents given in these examples are by weight unless otherwise indicated.
Example 1
Preparation of Di-p-chlorobenzylidene Sorbitol (I)
In a one liter round bottom flask equipped with overhead stirrer, nitrogen gas inlet, Dean-Stark trap, and condenser were placed 65.0 grams (0.25 mole) of 70 percent aqueous sorbitol, 70.3 grams (0.50 mole) of p-chlorobenzaldehyde, 1 5 milliliters of dimethylsulfoxide, 2.0 milliliters of 70 percent methanesulfonic acid, and 500 milliliters of cyclohexane. The mixture was stirred vigorously under a nitrogen atmosphere and heated to reflux. When the theoretical amount of water had distilled from the mixture the reaction was halted. During the reflux period a thick, white precipitate of the product formed. The precipitate was neutralized with triethylamine, filtered, washed thoroughly with water, and dried to give 66.2 grams of product as a white powder.The product was purified by suspending it in dioxane (10 percent w/v) and stirring the resulting mixture at 500C for 1 hour. The mixture was filtered, and the solid obtained was washed with additional dioxane and dried. The product had a melting point of 244--47 OC and was approximately 95 percent pure by high pressure liquid chromatography.
Example 2
Preparation of O-benzylidene-O-p-chlorobenzylidene Sorbitol (Il) O-benzylidene-O-p-chlorobenzylidene sorbitol (II) was prepared by the method of Example 1 using equimolar amounts of benzaldehyde and p-chlorobenzaldehyde. It was isolated as a mixture with dibenzylidene sorbitol (DBS) and di-p-chlorobenzylidene sorbitol (DCBS) as shown by high pressure liquid chromatography. The approximate ratio of DBS:II:DCBS was 1:3.8:2. The mixture melted at 207-2140C.
Example 3
Preparation of Mixture of Dibenzylidene Sorbitol and Di-p-chlorobenzylidene Sorbitol
A 50 percent mixture was prepared by mixing equal weights of commercially available dibenzylidene sorbitol and di-p-chlorobenzylidene sorbitol prepared by the method of Example 1.
Examples 4 and 5
Di-m-tolylidene sorbitol (Example 4) and di-p-tolylidene sorbitol (Example 5) disclosed in
Japanese Patent No. SHO 53 [1 978]-1 17044 to Kobayashi et al., (New Japan Chemical Co., Ltd.) were prepared from aqueous sorbitol and m-tolualdehyde and p-tolualdehyde respectively according to the method of Example 1. The respective melting points were 216-21 90C and 247-2480C.
Example 6
Di-m-bromobenzylidene sorbitol was prepared from aqueous sorbitol and m-bromobenzaldehyde according to the method of Example 1. The product had a melting point of 247-2500C.
Example 7
Bis(3,4,-dichlorobenzylidene)sorbitol was prepared from aqueous sorbitol and 3,4dichlorobenzaldehyde according to the method of Example 1. The melting point of the product was 2700C.
Example 8
Di-o-chlorobenzylidene sorbitol was prepared and purified by the method of Example 1 yielding a white solid with a melting point of 220-2220C. Incorporation of this material into polypropylene at 0.5 percent gave a haze value of 50.
Example 9
Di-p-methoxybenzylidene sorbitol was prepared and purified by the method of Example 1 yielding a white solid with a melting point of 185-1870C. Incorporation of this material into polypropylene at 0.5 percent gave a haze value of 52.
Example 10
Di-p-fluorobenzylidene sorbitol was prepared and purified by the method of Example 1 yielding a white solid of melting point 214-21 80C. Incorporation of this material into polypropylene at 0.25 percent gave a haze value of 17.
Example 11
Additives prepared pursuant to the preceding examples were incorporated into polypropylene by first preparating a concentrate containing the desired proportion of additive (either 3.75 grams for a .25 percent concentration or 7.50 for a .5 percent concentration) in 1 50 grams of a commercially available polypropylene and mixing in a laboratory blender. Then additional amounts of polypropylene powder (1350 grams) was added to the concentrate, with stirring at approximately 700 rpm in a Welex mixer, until the desired concentration of additive was achieved, e.g., either 0.25 percent or 0.5 percent as indicated in the Table. The mixture was then extruded at 465"F, pelletized and molded into thin plaques of about 50 mils at 4800 F.
The haze and clarity values were measured by ASTM Standard Test Method D1003-61 "Haze and iuminous transmittance of transparent plastics".
Table
Example Concentration
No. Additive Haze (%) Clarity{%) none 72
dibenzylidene sorbitol 0.25 16 73
0.25 10 79 } 0.38 9 9 di-p-chlorobenzyiidene sorbitol 4 0.50 8
0.75 9
1.00 10
2 O-benzylidene-O-p-chloro- 0.25 11 77
benzylidene sorbitol
3 mixture of dibenzylidene 0.25 12
sorbitol and di-p-chloro
benzylidene sorbitol
4 di-m-tolylidene sorbitol 0.25 12 76
5 di-p-tolylidene sorbitol 0.25 13 76
6 di-m-bromobenzylidene sorbitol 0.50 11
7 bis(3,4-dichlorobenzylidene) 0.50 8
sorbitol
8 di-o-chlorobenzylidene sorbitol 0.50 50
9 di-p-methoxybenzylidene sorbitol 0.50 52
10 di-p-fluorobenzylidene sorbitol 0.25 17
As the Table illustrates, compounds which are substituted in either or both of the meta and para positions with either chlorine or bromine atoms show a significant reduction in the haze or increase in clarity in the polypropylene samples beyond that provided by any prior clarifying agent including dibenzylidene sorbitol which is presently available commercially, and even di-m-toiylidene sorbitol and di-p-tolylidene sorbitol disclosed in the Japanese patent referred to above in Example 4. The mixed acetal of Example 2, furthermore, shows an unexpected reduction in haze over what would be anticipated from a compound containing one benzylidene moiety and one p-chlorobenzylidene moiety.
A priori it would be expected that compound of Example 2 would show a haze value intemediate between dibenzylidene sorbitol and di-p-chlorobenzylidene sorbitol. However, the compound shows a haze value much closer to that of di-p-chlorobenzylidene sorbitol. Likewise, the mixture of Example 3 shows a reduction of haze out of proportion to the concentration of the two components. Thus, at a composition of 50 percent dibenzylidene sorbitol and 50 percent di-p-chlorobenzylidene sorbitol the anticipated haze value would be half way between that of the two pure components. Instead, the mixture gives a reduction greater than that expected.
Claims (12)
1. A polyolefin composition which comprises a polymer selected from aliphatic polyolefins and copolymers containing at least one aliphatic olefin and one or more ethylenically unsaturated aliphatic monomers and the transparency of which has been improved by the inclusion of at least one di-acetal formed between one molecule of sorbitol and one molecule of a first benzaldehyde of the formula:
and one molecule of a second benzaldehyde (which may be the same as the first benzaldehyde) of the formula
wherein R, R1, R2, R3 and R4 are selected from hydrogen, lower alkyl, hydroxy, methoxy, mono- and dialkylamino, amino, nitro and halogen, with the proviso that at least one of R1, R2, R3 and R4 is chlorine or bromine.
2. A composition according to claim in which the di-acetal is selected from di-pchlorobenzylidene sorbitol; d-m-chlorobenzylidene sorbitol; O-benzylidene-O-p-chlorobenzylidene sorbitol; di-m-bromobenzylidene sorbitol and bis(3,4-dichlorobenzylidene) sorbitol.
3. A composition according to claim 1 in which the di-acetal is di-p-chlorobenzylidene sorbitol.
4. A composition according to any preceding claim in which the polymer comprises a homopolymer of an aliphatic monoolefin or a copolymer obtained by copolymerising an aliphatic monoolefin and one or more ethylenically unsaturated aliphatic monomers, and in which the aliphatic monoolefin contains from 2 to 6 carbon atoms and the homopolymer or copolymer has an average molecular weight of from 10,000 to 500,000.
5. A composition according to any preceding claim in which the polyolefin is polyethylene, polypropylene, poly 1-butene, polymethylpentene or ethylene propylene copolymer, optionally including up to 10% by weight of copolymerized ethylenically unsaturated aliphatic monomer.
6. A composition according to any preceding claim in which the amount of the di-acetal is from 0.01 to 2% by weight based on the weight of the composition.
7. A composition according to any preceding claim in which the di-acetal is substantially pure before being included in the composition.
8. A composition according to any preceding claim in which the di-acetal is included in the composition together with dibenzylidene sorbitol.
9. A composition according to any preceding claim which further includes at least one plasticiser selected from the group consisting of dioctyl phthalate, dibutyl phthalate, dioctyl sebacate, and dioctyl adipate.
10. A composition according to claim 1 substantially as herein described with reference to any of the examples.
11. An extruded or molded transparent article formed of a composition according to any preceding claim.
12. A novel compound which is a di-acetal formed between one molecule of sorbitol and one molecule of a first benzaldehyde of the formula
and one molecule of a second benzaldehyde (which may be the same as the first benzaldehyde) of the formula
wherein R, R1, R2, R3 and R4 are selected from hydrogen, lower alkyl, hydroxy, methoxy, mono- and dialkylamino, amino, nitro and halogen, with the proviso that at least one of R1, R2, R3 and R4 is chlorine or bromine.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14325880A | 1980-04-24 | 1980-04-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2077255A true GB2077255A (en) | 1981-12-16 |
| GB2077255B GB2077255B (en) | 1984-03-14 |
Family
ID=22503279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8112611A Expired GB2077255B (en) | 1980-04-24 | 1981-04-23 | Diacetals used in polyolefin compositions |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS56161444A (en) |
| BE (1) | BE888550A (en) |
| CA (1) | CA1161975A (en) |
| DE (1) | DE3116408C2 (en) |
| FR (1) | FR2481296B1 (en) |
| GB (1) | GB2077255B (en) |
| IT (1) | IT1143201B (en) |
| LU (1) | LU83317A1 (en) |
| MX (1) | MX158562A (en) |
| NL (1) | NL180842C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4483952A (en) * | 1982-04-23 | 1984-11-20 | E.C. Chemical Ind. Co., Ltd. | Polyolefin resin composition comprising a dibenzylidene sorbitol derivative |
| GB2140708A (en) * | 1983-03-24 | 1984-12-05 | Canon Kk | Ink-jet recording medium |
| US6297405B1 (en) | 2000-09-01 | 2001-10-02 | Milliken & Company | Fluorinated and chlorinated benzaldehydes |
| US6300525B1 (en) | 2000-09-01 | 2001-10-09 | Milliken & Company | Method of producing fluorinated and chlorinated benzaldehydes and compositions thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58180546A (en) * | 1982-04-19 | 1983-10-22 | Iic Kagaku Kogyo Kk | Acrylic resin molded article |
| JPS58180543A (en) * | 1982-04-19 | 1983-10-22 | Mitsubishi Petrochem Co Ltd | Propylene polymer composition |
| JPH0639554B2 (en) * | 1983-12-13 | 1994-05-25 | 三井東圧化学株式会社 | Transparent polypropylene resin container |
| JPS60127338A (en) * | 1983-12-13 | 1985-07-08 | Mitsui Toatsu Chem Inc | Container, made of polypropylene resin, and having good transparency |
| JPS60127336A (en) * | 1983-12-13 | 1985-07-08 | Mitsui Toatsu Chem Inc | Transparent blow molded container made of polypropylene |
| JPS60127335A (en) * | 1983-12-13 | 1985-07-08 | Mitsui Toatsu Chem Inc | Container made of polypropylene resin |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5122740A (en) * | 1974-08-16 | 1976-02-23 | Kenzo Hamada | |
| JPS5428348A (en) * | 1977-08-06 | 1979-03-02 | New Japan Chem Co Ltd | Modification of polyethylene |
| JPS54149752A (en) * | 1978-05-17 | 1979-11-24 | Mitsui Toatsu Chem Inc | Polyolefin resin composition for injection molding |
-
1981
- 1981-04-22 CA CA000375990A patent/CA1161975A/en not_active Expired
- 1981-04-23 IT IT48334/81A patent/IT1143201B/en active
- 1981-04-23 GB GB8112611A patent/GB2077255B/en not_active Expired
- 1981-04-23 MX MX186990A patent/MX158562A/en unknown
- 1981-04-23 NL NLAANVRAGE8102012,A patent/NL180842C/en not_active IP Right Cessation
- 1981-04-24 BE BE0/204596A patent/BE888550A/en not_active IP Right Cessation
- 1981-04-24 LU LU83317A patent/LU83317A1/en unknown
- 1981-04-24 FR FR8108241A patent/FR2481296B1/en not_active Expired
- 1981-04-24 JP JP6233181A patent/JPS56161444A/en active Granted
- 1981-04-24 DE DE3116408A patent/DE3116408C2/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4483952A (en) * | 1982-04-23 | 1984-11-20 | E.C. Chemical Ind. Co., Ltd. | Polyolefin resin composition comprising a dibenzylidene sorbitol derivative |
| GB2140708A (en) * | 1983-03-24 | 1984-12-05 | Canon Kk | Ink-jet recording medium |
| US6297405B1 (en) | 2000-09-01 | 2001-10-02 | Milliken & Company | Fluorinated and chlorinated benzaldehydes |
| US6300525B1 (en) | 2000-09-01 | 2001-10-09 | Milliken & Company | Method of producing fluorinated and chlorinated benzaldehydes and compositions thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3116408C2 (en) | 1984-09-27 |
| CA1161975A (en) | 1984-02-07 |
| IT1143201B (en) | 1986-10-22 |
| FR2481296B1 (en) | 1985-12-20 |
| JPS6140254B2 (en) | 1986-09-08 |
| NL8102012A (en) | 1981-11-16 |
| IT8148334A0 (en) | 1981-04-23 |
| FR2481296A1 (en) | 1981-10-30 |
| NL180842B (en) | 1986-12-01 |
| BE888550A (en) | 1981-10-26 |
| GB2077255B (en) | 1984-03-14 |
| JPS56161444A (en) | 1981-12-11 |
| DE3116408A1 (en) | 1982-01-28 |
| NL180842C (en) | 1987-05-04 |
| MX158562A (en) | 1989-02-15 |
| LU83317A1 (en) | 1981-07-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PE20 | Patent expired after termination of 20 years |
Effective date: 20010422 |